JPH03200828A - Polymer composition, and aqueous dispersion and water-based coating composition containing the same as emulsifier - Google Patents
Polymer composition, and aqueous dispersion and water-based coating composition containing the same as emulsifierInfo
- Publication number
- JPH03200828A JPH03200828A JP1339955A JP33995589A JPH03200828A JP H03200828 A JPH03200828 A JP H03200828A JP 1339955 A JP1339955 A JP 1339955A JP 33995589 A JP33995589 A JP 33995589A JP H03200828 A JPH03200828 A JP H03200828A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- water
- acid
- aqueous dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title claims abstract description 21
- 239000008199 coating composition Substances 0.000 title claims abstract description 7
- 239000006185 dispersion Substances 0.000 title claims description 30
- 239000003995 emulsifying agent Substances 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims abstract description 39
- -1 diol compound Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 9
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 19
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 11
- 239000002966 varnish Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000003010 ionic group Chemical group 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical group C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- OAKFFVBGTSPYEG-UHFFFAOYSA-N (4-prop-2-enoyloxycyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1CCC(OC(=O)C=C)CC1 OAKFFVBGTSPYEG-UHFFFAOYSA-N 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-n,3-n-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- HEBDGRTWECSNNT-UHFFFAOYSA-N 2-methylidenepentanoic acid Chemical compound CCCC(=C)C(O)=O HEBDGRTWECSNNT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CKSURTJJJBWBOU-UHFFFAOYSA-N 3-[(3-amino-3-imino-2-methylpropyl)diazenyl]-2-methylpropanimidamide;hydrochloride Chemical compound Cl.NC(=N)C(C)CN=NCC(C)C(N)=N CKSURTJJJBWBOU-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- MBRVKEJIEFZNST-UHFFFAOYSA-N 3-methyl-2-methylidenebutanoic acid Chemical compound CC(C)C(=C)C(O)=O MBRVKEJIEFZNST-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ONTAEZSXZGCILH-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)-methoxyamino]methanol Chemical compound CON(CO)C1=NC(N)=NC(N)=N1 ONTAEZSXZGCILH-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MDMKOESKPAVFJF-UHFFFAOYSA-N [4-(2-methylprop-2-enoyloxy)phenyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(OC(=O)C(C)=C)C=C1 MDMKOESKPAVFJF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- VUKHQPGJNTXTPY-UHFFFAOYSA-N but-2-enylbenzene Chemical compound CC=CCC1=CC=CC=C1 VUKHQPGJNTXTPY-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 229940113083 morpholine Drugs 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- KGLSETWPYVUTQX-UHFFFAOYSA-N tris(4-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound C1=CC(N=C=O)=CC=C1OP(=S)(OC=1C=CC(=CC=1)N=C=O)OC1=CC=C(N=C=O)C=C1 KGLSETWPYVUTQX-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0833—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups together with anionic or anionogenic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はウレタン結合を有しかつ両性イオン基を有する
高分子組成物、その存在下でエチレン性不飽和単量体を
重合してなる水性分散体およびその水性分散体を含有す
る水性塗料組成物に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a polymer composition having a urethane bond and an amphoteric ionic group, and an aqueous polymer composition obtained by polymerizing an ethylenically unsaturated monomer in the presence of the polymer composition. The present invention relates to a dispersion and an aqueous coating composition containing the aqueous dispersion.
（従来の技術）
アニオン性もしくはカチオン性を有する水分散性ウレタ
ンオリゴマーを乳化剤として使用して、エチレン性不飽
和単量体を乳化重合し、アクリル系エマルションワニス
を得る事は公知である（例えば、特開昭６１−２７２０
号公報）。このようにして得られたエマルションワニス
は、水性塗料に非常に有用である。(Prior Art) It is known that an acrylic emulsion varnish can be obtained by emulsion polymerizing ethylenically unsaturated monomers using an anionic or cationic water-dispersible urethane oligomer as an emulsifier (for example, Japanese Patent Publication No. 61-2720
Publication No.). The emulsion varnish thus obtained is very useful for water-based paints.
しかし、このエマルションワニスを合成するには、上記
水分散性ウレタンオリゴマーの界面活性能力だけでは安
定性が不充分であり、安定性を確保するためには多くの
場合低分子量の乳化剤をも添加しなければならない。こ
の結果、このエマルションワニスを使用した成型物、塗
膜は耐水性、耐候性で欠点を有する。又、他の原材料と
混合して使用する場合、凝集しやすく貯蔵安定性の面で
不満足である。However, in order to synthesize this emulsion varnish, the surface active ability of the water-dispersible urethane oligomer alone is insufficient for stability, and in many cases, a low molecular weight emulsifier is also added to ensure stability. There must be. As a result, molded products and coatings using this emulsion varnish have drawbacks in water resistance and weather resistance. Furthermore, when mixed with other raw materials, they tend to aggregate and are unsatisfactory in terms of storage stability.
（発明が解決しようとする課題）
本発明の目的は上記の欠点のいずれをも伴わない水性分
散体を製造するための新規なウレタン結合を有する高分
子組成物およびその存在下で単量体を乳化重合して得ら
れる水性分散体、並びにそれを含有してなる水性塗料組
成物を提供することである。OBJECTS OF THE INVENTION The object of the present invention is to provide a new polymeric composition with urethane bonds for the production of aqueous dispersions without any of the above-mentioned disadvantages, and to prepare monomers in the presence thereof. An object of the present invention is to provide an aqueous dispersion obtained by emulsion polymerization and an aqueous coating composition containing the same.
（課題を解決するための手段）
即ち、本発明は（ａ）末端ヒドロキシル基を有する分子
量ｌＯＯ〜５０００のジオール化合物、（ｂ）ジイソシ
アネート化合物、
（Ｃ）分子内に少なくとも１個の活性水素を有しかつ両
性イオン基を有する化合物および（ｄ）分子内に活性水
素を有するエチレン性不飽和単量体
をイソシアネートリッチの条件下に反応させてなる両性
イオン基含有オリゴマーを１級及び／もしくは２級ポリ
アミンを含有する水もしくは親水性溶剤を含む水媒体に
分散してなる高分子組成物を提供する。(Means for Solving the Problems) That is, the present invention provides (a) a diol compound having a terminal hydroxyl group and a molecular weight of 100 to 5000, (b) a diisocyanate compound, and (C) having at least one active hydrogen in the molecule. A compound having a zwitterionic group and (d) an ethylenically unsaturated monomer having an active hydrogen in the molecule are reacted under isocyanate-rich conditions to form a zwitterionic group-containing oligomer, which is a primary and/or secondary oligomer. A polymer composition is provided which is obtained by dispersing a polyamine in water or an aqueous medium containing a hydrophilic solvent.
本発明はまた上記高分子組成物を乳化剤として用いて、
エチレン性不飽和単量体を乳化重合することにより得ら
れる水性分散体を提供する。The present invention also uses the above polymer composition as an emulsifier,
An aqueous dispersion obtained by emulsion polymerization of an ethylenically unsaturated monomer is provided.
更に、本発明は上記水性分散体を含む水性塗料組成物を
提供する。Furthermore, the present invention provides an aqueous coating composition containing the above aqueous dispersion.
本発明に使用する末端ヒドロキシル基を有する分子ＩＩ
Ｉ ００〜５，０００のジオール化合物（ａ）は脂肪族
ジオール類；例えばエチレングリコール、プロパンジオ
ール、ネオペンチルグリコール、ブタンジオール、ヘキ
サンジオール、並びに１．２−アルキレンオキシドや同
様なエチレンオキシド、プロピレンオキシドを含む二価
アルコール、脂環式ジオール類：例えば１．４−シクロ
ヘキサンジオール、４，４°−ジヒドロキシシクロへキ
シル−２゜２−プロパン、ビス（エトキシル化）ビスフ
ェノールＡ１ビス（プロポキシル化）ビスフェノールＡ
等のエテロキシ原子数１〜２を含むアラリファチック二
価アルコール類、ポリエーテルジオール類：例えばポリ
エチレンオキシドジオール、ポリエチレンオキシドプロ
ピレンオキシドジオール、ポリプロピレンオキシドジオ
ール、ポリテトラメチレンオキシドジオール、上記のア
ルコール類とポリカルボン酸またはその無水物とのポリ
エステルジオール［ポリカルボン酸（好ましくはジカル
ボン酸）及びその無水物の例としてはマレイン酸、フマ
ル酸、メサコン酸、シトラコン酸、イタコン酸、グルタ
ル酸、アジピン酸、イソフタル酸、テレフタル酸等］。Molecules with terminal hydroxyl groups for use in the invention II
The diol compound (a) of I 00 to 5,000 is an aliphatic diol; for example, ethylene glycol, propanediol, neopentyl glycol, butanediol, hexanediol, as well as 1,2-alkylene oxide and similar ethylene oxide, propylene oxide. Dihydric alcohols and alicyclic diols including: e.g. 1,4-cyclohexanediol, 4,4°-dihydroxycyclohexyl-2°2-propane, bis(ethoxylated) bisphenol A1 bis(propoxylated) bisphenol A
Ararifatic dihydric alcohols and polyether diols containing 1 to 2 etheroxy atoms such as polyethylene oxide diol, polyethylene oxide propylene oxide diol, polypropylene oxide diol, polytetramethylene oxide diol, the above alcohols and polyether diols. Polyester diols with carboxylic acids or their anhydrides [Examples of polycarboxylic acids (preferably dicarboxylic acids) and their anhydrides include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaric acid, adipic acid, isophthalic acid] acids, terephthalic acid, etc.].
ポリカーボネート系及びポリカプロラクトン系のポリオ
ール類が挙げられる。Examples include polycarbonate-based and polycaprolactone-based polyols.
本発明に用いるジイソシアネート化合物（ｂ）の例とし
ては脂肪族、環状脂肪族、芳香脂肪族及び芳香族ジイソ
シアネート、例えば１．２−エチレンジイソシアネート
、１．４−テトラメチレンジイソシアネート、ｌ、６−
へキサメチレンジイソシアネート、２，２．４−または
２，４，４．−）リメチル−１，６−へキサメチレンジ
イソシアネート、１．１２−ドデカンジイソシアネート
、ω、ω−ジイソシアナートジブロビルエーテル、シク
ロブタン−１，３−ジイソシアネート、シクロヘキサン
−１，３−及び−１，４−ジイソシアネート、２．２−
及び−２，６−ジイツシアナート＝１−メチルーシクロ
ヘキサン、３−イソシアナートメチル−３，５，５−ト
リメチルシクロヘキシルイソシアネート（「イソホロン
ジイソシアネートＪ）、２゜５−及び３．５−ビス−（
イソシアナートメチル）８−メチル−１，４−メタノ−
デカヒドロナフタレン、１．５−１２．５−１ｔ、Ｓ−
及び２．６−ビス（イソシアナートメチル）−４，７−
メタノ−へキサヒトロインタン、ｌ、５−１２．５−１
ｌ。Examples of the diisocyanate compound (b) used in the present invention include aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates, such as 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-
Hexamethylene diisocyanate, 2,2.4- or 2,4,4. -) Limethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, ω,ω-diisocyanate dibrobyl ether, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1, 4-diisocyanate, 2.2-
and -2,6-diitsocyanato=1-methyl-cyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ("isophorone diisocyanate J"), 2.5- and 3.5-bis-(
Methyl isocyanate) 8-methyl-1,4-methano-
Decahydronaphthalene, 1.5-12.5-1t, S-
and 2,6-bis(isocyanatomethyl)-4,7-
Methano-hexahytrointane, l, 5-12.5-1
l.
６−及び２．６−ビス（イソシアナー））−４，７−メ
タノ−へキサヒドロインダン、ジシクロへキシル−２，
４゛−及び４．４゛−ジイソシアネート、２゜４−及び
２．６−へキサヒドロトルイレンジイソシアネート、パ
ーヒドロ−２，４°−及び−４，４゜−ジフェニルメタ
ンジイソシアネート、ω、ω゛−ジイソシアナートー１
．４−ジエチル−ベンゼン、１．３−及び１．４−フェ
ニレンジイソシアネート、４．４′−ジイソシアナート
−ジフェニル、４．４゜ジイソシアナート−３，３°−
ジクロロジフェニル、４．４′−ジイソシアナート−３
，３°−ジメトキシ−ジフェニル、４．４”−ジイソシ
アナート３．３”−ジメチル−ジフェニル、４．４°−
ジイソシアナート−３，３°−ジフェニル−ジフェニル
、２．４“−及び４．４°−ジイソシアナート−ジフェ
ニルメタン、ナフタレン−１，５−ジイソシアネート、
トルイレンジイソシアネート、例えば２゜４−または２
．６−）ルイレンージイソシアネート、Ｎ、Ｎ’−（４
，４−ジメチル−３，３°−ジイソシアナートジフェニ
ル）−ウレトジオン、ｍ−キシリレン−ジイソシアネー
ト、ジフェニルメタン２．４°−ジイソシアネート、ジ
フェニルメタン４．４°−ジイソシアネート、並びにト
リイソシアネート、例えば２，４．４’−トリイソシア
ナート−ジフェニルエーテル、４．４’、４”−トリイ
ソシアナートトリフェニルメタン、トリス（４−イソシ
アナートフェニル）−チオホスフェート、及びそれら異
性体の任意の混合物である。工業的に容易に得られる脂
肪族及び環状脂肪族ポリイソシアネート、特にヘキサメ
チレンジイソシアネート、４．４゛−ジ（イソシアナー
トシクロヘキシル）−メタン及び３−イソシアナート−
メチル−３，５，５トリメデルシクロヘキシルイソシア
ネートが好ましい。6- and 2,6-bis(isocyaner)-4,7-methano-hexahydroindane, dicyclohexyl-2,
4゛- and 4.4゛-diisocyanate, 2゜4- and 2.6-hexahydrotoluylene diisocyanate, perhydro-2,4゜- and -4,4゜-diphenylmethane diisocyanate, ω, ω゛-diisocyanate Isocyanate 1
．． 4-diethyl-benzene, 1,3- and 1,4-phenylene diisocyanate, 4,4'-diisocyanato-diphenyl, 4.4°-diisocyanate-3,3°-
Dichlorodiphenyl, 4,4'-diisocyanate-3
, 3°-dimethoxy-diphenyl, 4.4”-diisocyanate 3.3”-dimethyl-diphenyl, 4.4°-
Diisocyanate-3,3°-diphenyl-diphenyl, 2.4″- and 4.4°-diisocyanate-diphenylmethane, naphthalene-1,5-diisocyanate,
Toluylene diisocyanate, e.g. 2°4- or 2
．． 6-) Louislene diisocyanate, N, N'-(4
, 4-dimethyl-3,3°-diisocyanatodiphenyl)-uretdione, m-xylylene-diisocyanate, diphenylmethane 2.4°-diisocyanate, diphenylmethane 4.4°-diisocyanate, as well as triisocyanates, e.g. '-Triisocyanato-diphenyl ether, 4.4',4''-triisocyanatotriphenylmethane, tris(4-isocyanatophenyl)-thiophosphate, and any mixture of these isomers. Industrially easy. aliphatic and cycloaliphatic polyisocyanates obtained in
Methyl-3,5,5 trimedelcyclohexyl isocyanate is preferred.
本発明に用いる成分（ｃ）は分子内にイソシアネート基
と反応し得る活性水素基を少なくとも１個有し、かつ両
性イオン基を有する必要がある。活性水素基は酸素、窒
素または硫黄に結合した水素で、具体的にはヒドロキシ
ル基、カルボキシル基、アミノ基またはチオール基等が
挙げられる。好ましくはヒドロキシル基である。両性イ
オン基は酸性基および塩基性基の両方を含む基で、スル
ホベタイン基、ベタイン基、アミノ酸基が挙げられるが
、スルホベタイン基が好ましい。このような化合物の具
体例としては
８Ｏ−ＣＨｆＣＨ＊ −ＮＨ−ＣＯｔ ＣＨｔＳＯＪ−
（ＩＯ−ＣＨｔ ＣＨｔ ） ｔ ＮＣ）Ｉ ｔｃＨｔ
ｓＯｓＨ。Component (c) used in the present invention must have at least one active hydrogen group capable of reacting with an isocyanate group in its molecule, and must also have an amphoteric ionic group. The active hydrogen group is hydrogen bonded to oxygen, nitrogen, or sulfur, and specific examples thereof include hydroxyl group, carboxyl group, amino group, and thiol group. Preferably it is a hydroxyl group. The amphoteric ionic group is a group containing both an acidic group and a basic group, and examples thereof include a sulfobetaine group, a betaine group, and an amino acid group, with a sulfobetaine group being preferred. Specific examples of such compounds include 8O-CHfCH* -NH-COt CHtSOJ-
(IO-CHt CHt ) t NC)I tcHt
sOsH.
ＨＯ−ＣＨｔＣＨｔ−Ｎ（ＣＨｚＣＨｔＳＯｓＨ）ｔｌ
ＨＯ−ＣＨｔＣＨ＊＼
Ｎ−ＣＨ，Ｃ１１ｔＳＯ８Ｈ。HO-CHtCHt-N(CHzCHtSOsH)tl
HO-CHtCH*\N-CH, C11tSO8H.
／
ＨＣ
（ＨＯ−ＣＨｔ）ｓＣ−ＮＨ−ＣＨｔＣＨｔ−８ＯｓＨ
１１１０ｃＩＩ（ＣＨ３）ＣＩｌｆｆｉ−ＮＨ−ＣＨ２
Ｃｌ、５ＯｆｆＨ。/ HC (HO-CHt)sC-NH-CHtCHt-8OsH
1110cII(CH3)CIlffi-NH-CH2
Cl, 5OffH.
ＣＨ，０Ｈ
ＣＨ３＆Ｈ＊＋ ＋−ＣＩ−ＣＨ−Ｎｕ−（Ｊｌｔ−Ｃ
Ｈｔ−８ＯＪ。CH,0H CH3&H*+ +-CI-CH-Nu-(Jlt-C
Ht-8OJ.
Ｈ
ＣＨ３−（ＣＨ，）、−０−Ｃ８，−Ｃ１ｌ−ＣＨ，−
ＮＨ−ＣＩ、Ｃｕｔ−８Ｏ３Ｈ。H CH3-(CH,), -0-C8, -C1l-CH,-
NH-CI, Cut-8O3H.
Ｈ ００ＨＣＨ。H 00HCH.
（ＨＯ−ＣＨｔＣＨｔ）ｔＮｃＨ＊ｃＩ（ｘｃＯＯＨ等
が挙げられる。Examples include (HO-CHtCHt)tNcH*cI(xcOOH).
本発明に用いる成分（ｄ）は分子内に活性水素を有する
エチレン性不飽和単量体である。活性水素は上記成分（
Ｃ）で述べたものと同じであり、やはりヒドロキシル基
が好ましい。好適な単量体はヒドロキシエチルアクリレ
ート、ヒドロキシエチルメタクリレート、ヒドロキシプ
ロピルメタクリレート、Ｎ−メチロールアクリルアミド
およびヒドロキシエチル（メタ）アクリレートへのε−
カプロラクトンの付加体等が例示される。Component (d) used in the present invention is an ethylenically unsaturated monomer having active hydrogen in the molecule. Active hydrogen is the above component (
It is the same as mentioned in C), and hydroxyl group is also preferred. Suitable monomers are hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, N-methylolacrylamide and ε- to hydroxyethyl (meth)acrylate.
Examples include adducts of caprolactone.
本発明では上述の成分（ａ）〜（ｄ）をイソシアネート
リッチの条件下に反応させる。イソシアネートリッチの
条件下に反応させると、末端にイソシアネート基あるい
はエチレン性不飽和結合を有し、かつ両性イオン基が垂
下した両性イオン基含有ウレタンオリゴマーが得られる
。（ｂ）成分と（ａ） ＋ （Ｃ）＋（ｄ）成分の反応
比率はＮ Ｇ Ｏ（（ｂ）成分）：活性水素（（ａ）
＋（ｃ） ＋（ｄ）成分）等量比で１．０５：１〜６：
ｌで好ましくは１．１：１〜３：１で良好である。In the present invention, the above-mentioned components (a) to (d) are reacted under isocyanate-rich conditions. When the reaction is carried out under isocyanate-rich conditions, a zwitterionic group-containing urethane oligomer having isocyanate groups or ethylenically unsaturated bonds at the terminals and pendant amphoteric ionic groups is obtained. The reaction ratio of component (b) and component (a) + (C) + (d) is N GO (component (b)):active hydrogen ((a)
+ (c) + (d) component) equivalent ratio of 1.05:1 to 6:
1, preferably 1.1:1 to 3:1.
活性水素含有成分（（ａ） ＋ （ｃ） ＋（ｄ））中
、（ｃ）の量は活性水素等量で（ｃ）：（ａ）比率５：
１〜０．１：１で好ましくは２：１〜０．１：Ｉで良好
である。In the active hydrogen-containing component ((a) + (c) + (d)), the amount of (c) is equivalent to active hydrogen, and the ratio of (c): (a) is 5:
A ratio of 1 to 0.1:1 is preferable, and a ratio of 2:1 to 0.1:I is good.
又、（ｄ）の量は活性水素等量で（ｄ） ： （ａ）
＋ （ｃ）、比率で０．００１：１〜０．５：ｌで好ま
しくは０゜０１：Ｉ〜０．１：１で良好である。反応の
順序は特に特定されず、特定の順序で反応してもよく、
また４成分を同時に反応させてもよい。反応は５０〜１
１０℃で１〜３時間実施される。反応は通常溶媒、例え
ばベンゼン、キシレン、トルエン、メチルピロリドン、
酢酸ブチル、酢酸エチル、ジメチルホルムアミド中でも
しくは無溶媒で実施されるのがよい。Also, the amount of (d) is the active hydrogen equivalent (d): (a)
+ (c) A ratio of 0.001:1 to 0.5:l, preferably 0°01:I to 0.1:1, is good. The order of the reaction is not particularly specified, and the reactions may occur in a specific order.
Alternatively, the four components may be reacted simultaneously. The reaction is 50-1
It is carried out for 1-3 hours at 10°C. The reaction is usually carried out in a solvent such as benzene, xylene, toluene, methylpyrrolidone,
It is preferable to carry out the reaction in butyl acetate, ethyl acetate, dimethylformamide or without solvent.
上記両性イオン含有ウレタンオリゴマーを１級および／
または２級ポリアミンを含む水もしくは親水性溶媒中に
分散することにより、本発明の乳化剤として有用な高分
子組成物が得られる。好適なポリアミンとしては、エチ
レンジアミン、■。The above zwitterion-containing urethane oligomer is
Alternatively, a polymer composition useful as an emulsifier of the present invention can be obtained by dispersing it in water or a hydrophilic solvent containing a secondary polyamine. Suitable polyamines include ethylenediamine, ■.
２−プロピレンジアミン、１．３−メタンジアミン、イ
ソホロンジアミン、プロパン２．２−シクロヘキシルア
ミン、Ｎ、Ｎ’−ジメチル−〇−フェニレンジアミン、
Ｎ、Ｎ’−ジ−ｐ−トリル−ｍ−フェニレンジアミン、
Ｐ−アミノジフェニルアミン、ヒドラジン、置換ヒドラ
ジン、例えばジメチルヒドラジン、１．６−へキサメチ
レンビス−ヒドラジン等が挙げられる。親水性溶剤とし
ては、（エタノール）ｎ−プロパツール、イソプロパツ
ール、ｎ−ブタノール、イソブタノール、５ｅｃ−ブタ
ノール、ｔｅｒｔ−ブタノールなどのアルコール類、メ
チルセロソルブ、セロソルブ、ブチルセロソルブ、ブチ
ルカルピトールなどのエーテル類が挙げられる。2-propylenediamine, 1,3-methanediamine, isophoronediamine, propane 2,2-cyclohexylamine, N,N'-dimethyl-〇-phenylenediamine,
N,N'-di-p-tolyl-m-phenylenediamine,
P-aminodiphenylamine, hydrazine, substituted hydrazine, such as dimethylhydrazine, 1,6-hexamethylenebis-hydrazine, and the like. Hydrophilic solvents include (ethanol) alcohols such as n-propatool, isopropatool, n-butanol, isobutanol, 5ec-butanol, and tert-butanol, and ethers such as methyl cellosolve, cellosolve, butyl cellosolve, and butyl calpitol. Examples include:
上記高分子組成物中において、ポリアミンはウレタンオ
リゴマーと反応して、オリゴマーの鎖延長を行っている
ものと思われる。It is believed that in the above polymer composition, the polyamine reacts with the urethane oligomer to extend the chain of the oligomer.
得られた両性イオン含有ウレタンオリゴマー水分散体の
存在下で常法によりエチレン性不飽和単量体の乳化重合
を行う。乳化重合に使用するエチレン性不飽和単量体の
例としてはアクリロニトリル、メタクリレートリル等の
ニトリル；アクリルアミド、メタクリルアミド、ｎ−メ
チロールアクリルアミド等のアミド；メチルアクリレー
ト、エチルアクリレート、ブチルアクリレート、２−エ
チルヘキシルアクリレート等のアクリレート；メチルメ
タクリレート、エチルメタクリレート、ブチルメタクリ
レート等のアルキルアクリレート；アクリル酸、メタク
リル酸、マレイン酸、マロン酸、イタコン酸等の酸；ス
チレン、ビニルトルエン、α−メチルスチレン、メチル
ビニルトルエン等の芳香族炭化水素；２−又は４−ビニ
ルピリジン、２−メチル−５−ピリジン、５−エチル−
２ビニルピリジン等のピリジン；並びにこれらの混合物
を挙げることができる。また、単量体中に多官能性モノ
マー少量を導入すると塗料樹脂の性能が改善される。好
ましい多官能性モノマーの例としては、エチレングリコ
ールジアクリレート、グリセロールジアクリレート、ネ
オペンチルグリコールジメタクリレート、１．４−シク
ロヘキサン−ジオール−ジアクリレート、１．４−ベン
ゼン−ジオールジメタクリレート、ペンタエリトリトー
ルトリアクリレート等が挙げられる。重合は通常重合開
始剤の存在下に実施される。Emulsion polymerization of the ethylenically unsaturated monomer is carried out by a conventional method in the presence of the obtained aqueous dispersion of urethane oligomer containing amphoteric ions. Examples of ethylenically unsaturated monomers used in emulsion polymerization include nitriles such as acrylonitrile and methacrylate; amides such as acrylamide, methacrylamide, and n-methylolacrylamide; methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate; Acrylic acids such as acrylic acid, methacrylic acid, maleic acid, malonic acid, itaconic acid; Styrene, vinyltoluene, α-methylstyrene, methylvinyltoluene, etc. Aromatic hydrocarbons; 2- or 4-vinylpyridine, 2-methyl-5-pyridine, 5-ethyl-
Mention may be made of pyridine such as 2-vinylpyridine; as well as mixtures thereof. Also, the performance of coating resins is improved by incorporating small amounts of polyfunctional monomers into the monomers. Examples of preferred polyfunctional monomers include ethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol dimethacrylate, 1,4-cyclohexane-diol-diacrylate, 1,4-benzene-diol dimethacrylate, and pentaerythritol triacrylate. etc. Polymerization is usually carried out in the presence of a polymerization initiator.
重合開始剤としては、例えば過酸化ベンゾイル、ｔ−ブ
チルパーオキシド、クメンハイドロパーオキシドなどの
の有機過酸化物；アゾビスシアノ吉草酸、アゾビスイソ
ブチロニトリル、アゾビス（２，４−ジメチル）バレロ
ニトリル、アゾビス（２−アミジノプロパン）ハイドロ
クロライドなどの有機アゾ化合物；過硫酸カリウム、過
硫酸アンモニウム、過硫酸ナトリウム、過酸化水素など
の無機水溶性ラジカル開始剤；レドックス系開始剤など
が好適に使用できる。乳化重合は一般的な条件下で行な
われる。すなわち、エチレン性不飽和単量体の滴下重合
もしくは一部先仕込みでの滴下重合、もしくは本高分子
組成物で単量体を乳化分散し、その乳濁液を滴下重合し
ていくなど、あらゆる方法で可能である。尚、エチレン
性不飽和単量体に対する両性イオン含有ウレタンオリゴ
マーの重量比（固形分）は５〜９５／９５〜５が好まし
い。Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, t-butyl peroxide, and cumene hydroperoxide; azobiscyanovaleric acid, azobisisobutyronitrile, and azobis(2,4-dimethyl)valeronitrile. , azobis(2-amidinopropane) hydrochloride, and other organic azo compounds; inorganic water-soluble radical initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, and hydrogen peroxide; redox initiators, and the like can be suitably used. Emulsion polymerization is carried out under conventional conditions. In other words, various methods can be used, such as dropwise polymerization of ethylenically unsaturated monomers, dropwise polymerization with partial pre-preparation, or emulsification and dispersion of monomers with this polymer composition, and dropwise polymerization of the emulsion. It is possible in this way. The weight ratio (solid content) of the zwitterion-containing urethane oligomer to the ethylenically unsaturated monomer is preferably 5-95/95-5.
上記乳化重合を行なうことにより本発明の水性分散体が
得られる。この水性分散体組成物だけでも塗料用樹脂と
なりうるが、より高品質な塗料として（例えば自動車用
中上塗り塗料）使用する場合、水溶性樹脂と組み合わせ
る事が有利である。好ましくは、水溶性アクリル樹脂が
良好で高外観で高品質な塗膜が得られる。本発明に用い
る水溶性アクリル樹脂を構成するモノマ一種は酸性基を
有するエチレン性モノマー、ヒドロキシル基を有するエ
チレン性モノマーおよびこれらと共重合し得る他のエチ
レン性モノマーである。The aqueous dispersion of the present invention can be obtained by carrying out the above emulsion polymerization. This aqueous dispersion composition alone can be used as a coating resin, but when used as a higher quality coating (for example, as an intermediate top coating for automobiles), it is advantageous to combine it with a water-soluble resin. Preferably, the water-soluble acrylic resin is good, and a coating film with a high appearance and high quality can be obtained. The monomers constituting the water-soluble acrylic resin used in the present invention are an ethylenic monomer having an acidic group, an ethylenic monomer having a hydroxyl group, and other ethylenic monomers that can be copolymerized with these monomers.
酸性基を有するエチレン性モノマーの酸性基としてはカ
ルボキシル基、スルホン酸基等が挙げられる。カルボキ
シル基を有するエチレン性モノマーの例としては、アク
リル酸、メタクリル酸、クロトン酸、エタアクリル酸、
プロピルアクリル酸、イソプロピルアクリル酸、イタコ
ン酸、無水マレイン酸、フマール酸等が挙げられる。ス
ルホン酸基を有するエチレン性モノマーの例としては１
−ブチルアクリルアミドスルホン酸等が挙げられる。Examples of the acidic group of the ethylenic monomer having an acidic group include a carboxyl group and a sulfonic acid group. Examples of ethylenic monomers having carboxyl groups include acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid,
Examples include propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride, fumaric acid, and the like. Examples of ethylenic monomers having sulfonic acid groups are 1
-butylacrylamide sulfonic acid and the like.
酸性基を有するエチレン性モノマーの酸性基の一部はス
ルホン酸基であるのが好ましい。スルホン酸基は硬化促
進効果がある。It is preferable that some of the acidic groups of the ethylenic monomer having acidic groups are sulfonic acid groups. Sulfonic acid groups have a curing accelerating effect.
ヒドロキシル基を有するエチレン性モノマーの例として
は、アクリル酸ヒドロキシエチル、アクリル酸ヒドロキ
シプロピル、アクリル酸ヒドロキシブチル、メタクリル
酸ヒドロキシメチル、メタクリル酸ヒドロキシエチル、
メタクリル酸ヒドロキシプロピル、メタクリル酸ヒドロ
キシブチル、Ｎ−メチロールアクリルアミド、アリルア
ルコール等が挙げられる。Examples of ethylenic monomers having a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate,
Examples include hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-methylolacrylamide, allyl alcohol, and the like.
他のエチレン性モノマーの例としてはアクリル酸アルキ
ルエステル（アクリル酸メチル、アクリル酸エチル、ア
クリル酸イソプロピル、アクリル酸ｎ−プロピル、アク
リル酸ｎ−ブチル、アクリル酸ｔ−ブチル、アクリル酸
２−エチルヘキシル、アクリル酸ｎ−オクチル、アクリ
ル酸ラウリルなど）、メタクリル酸アルキルエステル（
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸イソプロピル、メタクリル酸ｎ−プロピル、メタクリ
ル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル
酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタ
クリル酸ｎ−オクチル、メタクリル酸ラウリル、メタク
リル酸ステアリル、メタクリル酸トリデシルなど）、油
脂脂肪酸とオキシラン構造を有するアクリル酸またはメ
タクリル酸エステルモノマーとの付加反応物（例ニステ
アリン酸とグリシジルメタクリレートの付加反応物）、
Ｃ，１以上のアルキル基を含むオキシラン化合物とアク
リル酸またはメタクリル酸との付加反応物（例：日本特
許第５８３，１８５号、同第６０９，３２２号）、スチ
レン、α−メチルスチレン、０−メチルスチレン、ｎ−
メチルスチレン、ｐ−メチルスチレン、１）−ｔｅｒｔ
−ブチルスチレン、アクリル酸ベンジル、メタクリル酸
ベンジル、イタコン酸エステル（イタコン酸ジメチルな
ど）、マレイン酸エステル（マレイン酸ジメチルなど）
、フマール酸エステル（フマール酸ジメチルなど）、ア
クリロニトリル、メタクリロニトリル、酢酸ビニル等が
挙げられる。Examples of other ethylenic monomers include acrylic acid alkyl esters (methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, etc.), alkyl methacrylate ester (
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate, etc.), addition reaction products of fat and oil fatty acids and acrylic acid or methacrylic acid ester monomers having an oxirane structure (e.g. addition reaction products of nistearic acid and glycidyl methacrylate),
C, addition reaction product of oxirane compound containing one or more alkyl group and acrylic acid or methacrylic acid (e.g. Japanese Patent Nos. 583,185 and 609,322), styrene, α-methylstyrene, 0- methylstyrene, n-
Methylstyrene, p-methylstyrene, 1)-tert
-Butylstyrene, benzyl acrylate, benzyl methacrylate, itaconate esters (dimethyl itaconate, etc.), maleate esters (dimethyl maleate, etc.)
, fumaric acid esters (such as dimethyl fumarate), acrylonitrile, methacrylonitrile, and vinyl acetate.
上記３種のモノマーを通常の方法で重合することにより
共重合体が得られる。例えば、モノマー配合物を公知の
重合触媒と混合し、重合可能な温度に加熱した溶剤を含
む反応容器中へ添加、熟成することにより共重合体を得
ることができる。A copolymer can be obtained by polymerizing the above three types of monomers in a conventional manner. For example, a copolymer can be obtained by mixing a monomer blend with a known polymerization catalyst, adding the mixture to a reaction vessel containing a solvent heated to a polymerizable temperature, and aging the mixture.
上記共重合体樹脂の水性化は常法に従って、カルボキシ
ル基の如き酸性基を塩基性物質、例えばモノメチルアミ
ン、ジメチルアミン、トリメチルアミン、モノエチルア
ミン、トリエチルアミン、モノイソプロピルアミン、ジ
イソプロピルアミン、ジエチレントリアミン、トリエチ
レンテトラミン、モノエタノールアミン、ジェタノール
アミン、トリエタノールアミン、モノイソプロパツール
アミン、ジイソプロパツールアミン、ジメチルエタノー
ルアミン、モルホリン、メチルモルホリン、ピペラジン
、アンモニア、水酸化ナトリウム、水酸化カリウム、水
酸化リチウム等で中和することにより行なわれる。The above-mentioned copolymer resin is made water-soluble by replacing acidic groups such as carboxyl groups with basic substances such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, triethylamine, monoisopropylamine, diisopropylamine, diethylenetriamine, and triethylenetetramine. , monoethanolamine, jetanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, dimethylethanolamine, morpholine, methylmorpholine, piperazine, ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. This is done by neutralizing it with
本発明の水性分散体と水溶性アクリル樹脂の重量比は５
〜９０／９５〜１０が好適である。得られた組成物（１
）の酸価は１５〜１００が好ましく、ヒドロキシル価は
３０〜１００が好ましい。この酸価およびヒドロキシル
価を提供するものは前述の共重合体の酸性基およびヒド
ロキシル基によるところが大きく、共重合体合成のため
のモノマーはこの樹脂組成物の酸価およびヒドロキシル
価を上記範囲内に入るような量で用いられる。酸価が１
５以下の場合は水分散安定性が悪く、１００を越えると
水溶解性が悪く、塗膜の耐水性が低下する。ヒドロキシ
ル価が３０未満であると塗膜の架橋密度が低く、耐水性
も悪くなる。２００を越えると塗膜の耐水性が不足する
。また必要により硬化剤としてアミノ化合物もしくはブ
ロックイソシアネート化合物もしくはエポキシ化合物を
添加すればよい。アミノ化合物としてはアルコキシ化メ
ラミンホルムアルデヒド縮合物（メラミンホルムアルデ
ヒドまたはパラホルムアルデヒドとの縮合物であり、例
えばメトキシメチロールメラミン、イソブトキシ化メチ
ロールメラミン、ｎ−ブトキシ化メチロールメラミン）
等が挙げられる。エポキシ化合物としては２つ以上のエ
ポキシド基を含有する脂環式系もしくは芳香族系、脂肪
族系エポキシド化合物（例えば、シェルケミカル社製の
エピコート８２８、エピコート１００１．エピコート＋
００４、共栄油脂社製のエボライト４０Ｅ１エボライト
４００Ｅ１エボライト＃１６００、エボライト＃７２１
等）等が挙げられ、これらの少なくとも１種を使用する
。The weight ratio of the aqueous dispersion of the present invention to the water-soluble acrylic resin is 5
-90/95-10 is suitable. The resulting composition (1
) preferably has an acid value of 15 to 100, and a hydroxyl value of 30 to 100. What provides this acid value and hydroxyl value is largely due to the acidic group and hydroxyl group of the above-mentioned copolymer, and the monomer for copolymer synthesis is used to maintain the acid value and hydroxyl value of this resin composition within the above range. It is used in the amount that fits. acid value is 1
When it is less than 5, water dispersion stability is poor, and when it exceeds 100, water solubility is poor and the water resistance of the coating film is reduced. If the hydroxyl value is less than 30, the crosslinking density of the coating film will be low and the water resistance will also be poor. If it exceeds 200, the water resistance of the coating film will be insufficient. If necessary, an amino compound, a blocked isocyanate compound, or an epoxy compound may be added as a curing agent. Amino compounds include alkoxylated melamine formaldehyde condensates (condensates with melamine formaldehyde or paraformaldehyde, such as methoxymethylolmelamine, isobutoxylated methylolmelamine, n-butoxylated methylolmelamine);
etc. Examples of epoxy compounds include alicyclic, aromatic, or aliphatic epoxide compounds containing two or more epoxide groups (e.g., Epikoat 828, Epicoat 1001, Epicoat + manufactured by Shell Chemical Co., Ltd.).
004, Evolite 40E1 Evolite 400E1 Evolite #1600, Evolite #721 manufactured by Kyoei Yushi Co., Ltd.
etc.), and at least one of these is used.
又、必要により着色剤やアルミニウムなどの金属顔料を
添加してもよく、金属顔料の場合水性メタリック塗料と
なり、メタル配向がよく高外観のメタリック塗膜が得ら
れる。Further, if necessary, a colorant or a metal pigment such as aluminum may be added. In the case of a metal pigment, a water-based metallic paint is obtained, and a metallic paint film with good metal orientation and a high appearance can be obtained.
又、着色剤を含有しない水性塗料についてクリヤー塗料
として使用できメタリック塗料、ソリッドカラー塗料等
のオーバーコート用塗料として使用される。特に、メタ
リック塗料上へのオーバーコートでは一般にウェット・
オン・ウェット塗装と呼ばれているがメタリック塗膜を
焼付は硬化させずクリヤー塗料を塗装し同時に焼付は硬
化させる方式である。本発明の水性メタリック塗料およ
び水性クリヤー塗料については単独使用および両方使用
とも良好な性能を示す。又、これらの組成物は、特異な
粘性をもち塗装時のタレ性も非常に良好である。Furthermore, it can be used as a clear paint for water-based paints that do not contain colorants, and can be used as an overcoat paint for metallic paints, solid color paints, etc. In particular, overcoating over metallic paints generally requires a wet coating.
It is called on-wet painting, but it is a method in which the metallic coating is not hardened by baking, but a clear paint is applied and at the same time hardening is done by baking. The water-based metallic paint and water-based clear paint of the present invention show good performance when used alone or when both are used. In addition, these compositions have a unique viscosity and exhibit very good sagging properties during coating.
（実施例）
本発明を実施例により更に詳細に説明する。本発明はこ
れら実施例に限定されるものと解してはならない。(Example) The present invention will be explained in more detail with reference to Examples. The present invention should not be construed as being limited to these examples.
実施例１
ウレタンプレポリマーの合成
温度計、撹拌機、コンデンサーを備えた５００叶の反応
容器にＮ、Ｎ−ジヒドロキシエチルアミノエタンスルホ
ン酸（ｎｐ、 １５３℃）１２．７８重量部、トリエチ
ルアミン９．０９重量部、Ｎ−メチルピロリドン６２．
４重量部を加え９０℃に加熱し溶解させた。次に、イソ
ホロンジイソシアネート８６．６重量部とポリプロピレ
ングリコール（水酸基価、１１２、分子量１．０００）
７５重量部を加え１０分間撹拌後、ジブチル錫ジラウレ
ート０゜０８重量部を加えた。次に、９５℃まで昇温し
、１時間反応させた。その後、６０℃まで冷却後ヒドロ
キシエチルメタクリレート１．５８重量部を加え６０℃
で２時間反応させた。冷却後、メチルメタクリレート２
０．４重量部ｎ−ブチルアクリレート２０．１重量部で
希釈しウレタンプレポリマー溶液を得た。Example 1 Synthesis of urethane prepolymer 12.78 parts by weight of N,N-dihydroxyethylaminoethanesulfonic acid (np, 153°C) and 9.09 parts by weight of triethylamine were placed in a 500mm reaction vessel equipped with a thermometer, stirrer, and condenser. Parts by weight, N-methylpyrrolidone 62.
4 parts by weight were added and heated to 90°C to dissolve. Next, 86.6 parts by weight of isophorone diisocyanate and polypropylene glycol (hydroxyl value, 112, molecular weight 1.000)
After adding 75 parts by weight and stirring for 10 minutes, 0.08 parts by weight of dibutyltin dilaurate was added. Next, the temperature was raised to 95° C., and the mixture was reacted for 1 hour. Then, after cooling to 60°C, 1.58 parts by weight of hydroxyethyl methacrylate was added and the mixture was heated to 60°C.
The mixture was allowed to react for 2 hours. After cooling, methyl methacrylate 2
It was diluted with 0.4 parts by weight of n-butyl acrylate and 20.1 parts by weight to obtain a urethane prepolymer solution.
水性不飽和二重結合含有高分子組成物の合成温度計、撹
拌機、コンデンサー、滴下ロートを備えた１、０００３
１１２の反応容器に脱イオン水２２７重量部、ヒドラジ
ン水和物３．１重量部を加え撹拌下、上記ウレタンプレ
ポリマー溶液１３６゜４重量部を添加した。その後、３
０分撹拌をおこなった。得られた組成物は白濁した安定
な水分散体であった。Synthesis of aqueous unsaturated double bond-containing polymer composition 1,0003 equipped with thermometer, stirrer, condenser, and dropping funnel
227 parts by weight of deionized water and 3.1 parts by weight of hydrazine hydrate were added to a No. 112 reaction vessel, and while stirring, 136.4 parts by weight of the above urethane prepolymer solution was added. After that, 3
Stirring was performed for 0 minutes. The resulting composition was a cloudy, stable aqueous dispersion.
実施例２
水性分散体組成物の合成
温度計、撹拌機、コンデンサー、滴下ロートを備えた１
、０００１１２の反応容器に上記水性不飽和二重結合含
有高分子組成物３６７重量部を加え、つぎに過硫酸カリ
ウム水溶液（過硫酸カリウム／脱イオン水；０．６／１
３０）１３０．６重量部を加えよく撹拌した。次に、９
０℃まで昇温し、メチルメタクリレート６０重量部およ
びｎ−ブチルアクリレート６０重量部のモノマー混合液
を１時間で滴下導入した。滴下終了後、過硫酸カリウム
水溶液（過硫酸カリウム／脱イオン水、０．１／２０）
２０．１重量部を添加し、さらに１時間撹拌を継続した
。冷却後、４００メツシユの濾過をし、安定な水性分散
体を得た。Example 2 Synthesis of aqueous dispersion composition 1 equipped with a thermometer, stirrer, condenser, and dropping funnel
, 000112, 367 parts by weight of the above aqueous unsaturated double bond-containing polymer composition was added, and then a potassium persulfate aqueous solution (potassium persulfate/deionized water; 0.6/1
30) 130.6 parts by weight was added and stirred well. Next, 9
The temperature was raised to 0°C, and a monomer mixture of 60 parts by weight of methyl methacrylate and 60 parts by weight of n-butyl acrylate was introduced dropwise over 1 hour. After dropping, add potassium persulfate aqueous solution (potassium persulfate/deionized water, 0.1/20)
20.1 parts by weight was added, and stirring was continued for an additional hour. After cooling, it was filtered through 400 meshes to obtain a stable aqueous dispersion.
実施例３
撹拌機、温度調節機、冷却管を備えた１１２の反応容器
にエチレングリコールモノブチルエーテル７６重量部を
仕込み、更にスチレン４．５重量部、メチルメタクリレ
ート６３重量部、２−ヒドロキシエチルメタクリレート
４８重量部、ｎ−ブチルアクリレート１１７重量部、メ
タクリル酸２７重量部およびアゾビスイソブチロニトリ
ル３重量部からなるモノマー溶液６１重量部を添加して
撹拌下、温度を１２０℃にした。上記モノマー溶液２４
５重量部を３時間で添加した後、１時間撹拌を継続した
。更にジメチルエタノールアミン２８部と脱イオン水２
００部を添加して揮発分５０％、樹脂の数平均分子量１
２．０００のアクリル樹脂ワニスを得た。この樹脂は０
８価７０、酸価５８を有した。Example 3 76 parts by weight of ethylene glycol monobutyl ether was charged into a 112 reaction vessel equipped with a stirrer, a temperature controller, and a cooling tube, and 4.5 parts by weight of styrene, 63 parts by weight of methyl methacrylate, and 48 parts by weight of 2-hydroxyethyl methacrylate were added. 61 parts by weight of a monomer solution consisting of 117 parts by weight of n-butyl acrylate, 27 parts by weight of methacrylic acid and 3 parts by weight of azobisisobutyronitrile were added, and the temperature was brought to 120° C. with stirring. The above monomer solution 24
After adding 5 parts by weight over 3 hours, stirring was continued for 1 hour. Additionally, 28 parts of dimethylethanolamine and 2 parts of deionized water
00 parts, volatile content 50%, number average molecular weight of resin 1
2.000 acrylic resin varnish was obtained. This resin is 0
It had an 8 valence of 70 and an acid value of 58.
この樹脂ワニス１４０重量部にサイメル３０３（三井東
圧社製メトキシ化メチロールメラミン）３０重量部を添
加した。To 140 parts by weight of this resin varnish, 30 parts by weight of Cymel 303 (methoxylated methylolmelamine manufactured by Mitsui Toatsu Co., Ltd.) was added.
メタリック塗料の調製
上記樹脂ワニス１７０重量部に実施例１で得られた水性
分散体を樹脂固型分で５０重量部（ワニスとして１２５
重量部）およびアルミニウム顔料を金属分で１５重量部
撹拌混合し次いで脱イオン水で希釈しＮｏ、４フオード
カツプで２５〜３０秒（２０℃）になるまで希釈しメタ
リック塗料とした。Preparation of Metallic Paint Add the aqueous dispersion obtained in Example 1 to 170 parts by weight of the above resin varnish and add 50 parts by weight of resin solids (125 parts by weight as varnish).
(parts by weight) and aluminum pigment were stirred and mixed in a metal content of 15 parts by weight, and then diluted with deionized water and diluted with a No. 4 food cup for 25 to 30 seconds (at 20 DEG C.) to obtain a metallic paint.
水性クリアー塗料の調製
メタリック塗料樹脂と同様にｎ−ブチルアクリレート６
５．８重量部、メチルメタクリレート１１．８重量部、
２−ヒドロキシエチルメタクリレート１６．２重量部、
メタクリル酸６１重量部およびアゾビスイソブチロニト
リル５重量部、また溶媒としてブチルジグリコールを用
いて重合体を合成した。この樹脂をジメチルエタノール
アミンで１００％中和した。この重合体は０８価７０お
よび酸価４０を有した。Preparation of water-based clear paintN-butyl acrylate 6 as well as metallic paint resin
5.8 parts by weight, 11.8 parts by weight of methyl methacrylate,
16.2 parts by weight of 2-hydroxyethyl methacrylate,
A polymer was synthesized using 61 parts by weight of methacrylic acid, 5 parts by weight of azobisisobutyronitrile, and butyl diglycol as a solvent. This resin was 100% neutralized with dimethylethanolamine. This polymer had an 08 value of 70 and an acid value of 40.
得られた樹脂ワニスをサイメル３０３を架橋剤と使用し
、その樹脂固形分比が７０／３０となるように配合し、
脱イオン水を用いてＮｏ、４フオードカツプで３０〜３
５秒（２０℃）になるまで希釈し、水性クリアー塗料と
した。The obtained resin varnish was blended using Cymel 303 as a crosslinking agent so that the resin solid content ratio was 70/30,
No. 30-3 with 4 food cups using deionized water
It was diluted to 5 seconds (20°C) to obtain a water-based clear paint.
塗装実験例１
中塗り鋼板に上記実施例３で調製したメタリック塗料、
次いで水性クリアー塗料を乾燥塗膜で前者２０μ、後者
３０μとなるように温度２３℃、温度６０％の環境下で
エアースプレー塗装した。Painting Experiment Example 1 Metallic paint prepared in Example 3 above on intermediate coated steel plate,
Next, a water-based clear paint was air-sprayed at a temperature of 23° C. and a temperature of 60% so that the dry film thickness of the former was 20 μm and the latter was 30 μm.
前者をインターバル１分間でツーステージで塗布し、そ
の後５分間の乾燥をし、次いでワンステージで後者を塗
装した後、７分間セツティングした。The former was applied in two stages with an interval of 1 minute, followed by 5 minutes of drying, and then the latter was applied in one stage and allowed to set for 7 minutes.
次いで、塗装板を乾燥機で１５０℃２０分間焼き付けし
、試験板を作成した。この塗膜の付着性および塗膜外観
を評価した。結果を表−ｌに示す。Next, the coated plate was baked in a dryer at 150°C for 20 minutes to prepare a test plate. The adhesion and appearance of this coating film were evaluated. The results are shown in Table 1.
尚、中塗り鋼板は脱脂化成処理を行なった磨き軟鋼板に
自動車用電着塗料を塗装後焼き付けその後自動車用中塗
り塗料を塗布、焼き付けたものを使用した。The intermediate coated steel plate used was a polished mild steel plate that had been subjected to a degreasing chemical conversion treatment, coated with an automotive electrodeposition paint, baked, and then coated with an automotive intermediate paint and baked.
表−ｌ
（付着性の評価方法）
カッターナイフでクロスカットを入れテープによる剥離
テストを行なった。○は剥離なし、×は剥離有りを示す
。Table 1 (Method for evaluating adhesion) A cross cut was made with a utility knife and a peel test was performed using tape. ○ indicates no peeling, and × indicates peeling.
実施例４
ウレタンプレポリマーの合成
Ｎ、気流下、温度計、撹拌機、コンデンサーを備えたＩ
Ｑの反応容器にＮ、Ｎ−ジヒドロキシエチルアミノスル
ホン酸（ｍｐ： １５３℃）：４２．６重量部、トリエ
チルアミン：３０．３重量部、Ｎ−メチルピロリドン＝
２０８重量部、を加え９５℃に加熱し廖解させる。次に
、イソホロンジイソシアネート：１６６．５重量部とポ
リプロピレングリコール（水酸基価：１１２．２、分子
量：１０００）：２００重量部とポリプロピレングリコ
ール（水酸基価：５６．１．分子量：２０００）：１６
０重量部を加え１０分間撹拌後、ノブチル錫ジラウレー
ト：０２８重量部を加える。次に、９５℃まで昇温し、
１時間反応させる。その後、６０℃まで冷却後、ヒドロ
キシエチルメタクリレート：５．２重量部とヒドロキノ
ンモノメチルエーテル：０．２８重Ｎ部を加え、６０℃
で２時間反応させる。冷却後、メチルメタクリレート：
４５重量部、ｎ−ブチルアクリレート二９０重量部で希
釈し、ウレタンプレポリマー溶液を得た。Example 4 Synthesis of urethane prepolymer N, under air flow, I equipped with thermometer, stirrer and condenser
In reaction vessel Q, N,N-dihydroxyethylaminosulfonic acid (mp: 153°C): 42.6 parts by weight, triethylamine: 30.3 parts by weight, N-methylpyrrolidone =
Add 208 parts by weight and heat to 95°C to dissolve. Next, 166.5 parts by weight of isophorone diisocyanate, 200 parts by weight of polypropylene glycol (hydroxyl value: 112.2, molecular weight: 1000) and 16 parts by weight of polypropylene glycol (hydroxyl value: 56.1, molecular weight: 2000)
After adding 0 parts by weight and stirring for 10 minutes, 028 parts by weight of butyltin dilaurate was added. Next, the temperature was raised to 95°C,
Let react for 1 hour. Then, after cooling to 60°C, 5.2 parts by weight of hydroxyethyl methacrylate and 0.28 parts by weight of hydroquinone monomethyl ether were added, and the mixture was heated to 60°C.
Let it react for 2 hours. After cooling, methyl methacrylate:
It was diluted with 45 parts by weight and 290 parts by weight of n-butyl acrylate to obtain a urethane prepolymer solution.
水性不飽和二重結合含有高分子組成物の合成Ｎ、気流下
、温度計、撹拌機、コンデンサー滴下ロートを備えたＩ
Ｑの反応容器に脱イオン水：３４２．９重量部、ヒドラ
ジン−水和物２１．８重Ｍ部を加え撹拌下、上記ウレタ
ンプレポリマー溶１ｆｆｌ：１３５．５重量部を添加し
た。その後、３０分撹拌を行なった。得られた組成物は
白濁した安定な水分散体であった。Synthesis of aqueous unsaturated double bond-containing polymer composition N, under air flow, equipped with a thermometer, stirrer, and condenser dropping funnel I
342.9 parts by weight of deionized water and 21.8 parts by weight of hydrazine hydrate were added to a reaction vessel Q, and while stirring, 1ffl of the above urethane prepolymer solution: 135.5 parts by weight was added. Thereafter, stirring was performed for 30 minutes. The resulting composition was a cloudy, stable aqueous dispersion.
水性分散体組成物の合成
Ｎ、気流下、温度計、撹拌機、コンデンサー滴下ロート
を備えた１１２の反応溶液に上記水性不飽和二重結合含
有高分子組成物：４８０．２重量部を加え、次に、過硫
酸カリウム水溶液（過硫酸カリウム／脱イオン水−１１
５０９）：３５７重量部を加え、よく撹拌する。次に、
９０℃まで昇温し、メチルメタクリレート：４８．３重
量部とｎ−ブチルアクリレート：９６．７重量部のモノ
マー混合液を１時間で滴下導入した。滴下終了後、過硫
酸カリウム水溶液（過硫酸カリウム／脱イオン水＝ｌ／
６９）：Ｉ １．２重量部を添加し、さらに１時間撹拌
を継続した。冷却後、４００メツシユの濾過をし、安定
な水性分散体組成物を得た。Synthesis of aqueous dispersion composition 480.2 parts by weight of the above aqueous unsaturated double bond-containing polymer composition was added to a reaction solution of 112 equipped with a thermometer, a stirrer, and a condenser dropping funnel under an air stream. Next, a potassium persulfate aqueous solution (potassium persulfate/deionized water-11
509): Add 357 parts by weight and stir well. next,
The temperature was raised to 90°C, and a monomer mixture of 48.3 parts by weight of methyl methacrylate and 96.7 parts by weight of n-butyl acrylate was introduced dropwise over 1 hour. After dropping, add potassium persulfate aqueous solution (potassium persulfate/deionized water = l/
69):I was added in an amount of 1.2 parts by weight, and stirring was continued for an additional hour. After cooling, it was filtered through 400 meshes to obtain a stable aqueous dispersion composition.
実施例５
ウレタンプレポリマーの合成
Ｎ、気流下、温度計、撹拌機、コンデンサーを備えた２
Ｑの反応容器にＮ、Ｎ−ジヒドロキシエチルアミノスル
ホン酸（ｍｐ： １５３℃）：３４．１重量部、ジメチ
ロールプロピオン酸：２１．４重量部、トリエチルアミ
ン＝４８．５重量部、Ｎ−メチルピロリドン・３２０重
量部を加え９０℃に加熱し溶解させる。次に、イソホａ
ンジイソシアネート：３５５２重量部とポリプロピレン
グリコール（水酸基価：１１２．２、分子量：１０００
）：２８８重量部とポリプロピレングリコール（水酸基
価：５６゜１、分子量：２０００）：３２０重量部を加
え１０分間撹拌後、ジブチル錫ジラウレート：０．５３
重量部を加える。次に、９５℃まで昇温し、１時間反応
させる。その後、６０℃まで冷却後、ヒドロキシエチル
メタクリレート＝８．３重量部とヒドロキノンモノメチ
ルエーテル：０．５３重量部を加え、６０℃で２時間反
応させる。冷却後、メチルメタクリレート：１０８．８
重量部、ｎ−ブチルアクリレート：Ｉ Ｏ７，２重量部
で希釈し、ウレタンプレポリマー溶液を得た。Example 5 Synthesis of urethane prepolymer N, under air flow, equipped with thermometer, stirrer, condenser 2
In reaction vessel Q, N,N-dihydroxyethylaminosulfonic acid (mp: 153°C): 34.1 parts by weight, dimethylolpropionic acid: 21.4 parts by weight, triethylamine = 48.5 parts by weight, N-methylpyrrolidone. - Add 320 parts by weight and heat to 90°C to dissolve. Next, Isoho a
diisocyanate: 3552 parts by weight and polypropylene glycol (hydroxyl value: 112.2, molecular weight: 1000
): 288 parts by weight and polypropylene glycol (hydroxyl value: 56°1, molecular weight: 2000): 320 parts by weight were added, and after stirring for 10 minutes, dibutyltin dilaurate: 0.53
Add parts by weight. Next, the temperature is raised to 95° C. and the mixture is reacted for 1 hour. Thereafter, after cooling to 60°C, 8.3 parts by weight of hydroxyethyl methacrylate and 0.53 parts by weight of hydroquinone monomethyl ether were added, and the mixture was reacted at 60°C for 2 hours. After cooling, methyl methacrylate: 108.8
Part by weight, n-butyl acrylate:IO was diluted with 7.2 parts by weight to obtain a urethane prepolymer solution.
水性不飽和二重結合含有高分子組成物の合成Ｎ、気流下
、温度計、撹拌機、コンデンサー滴下ロートを備えた１
１２の反応容器に脱イオン水：３８０重量部、エチレン
ジアミン＝６重量部を加え撹拌下、上記ウレタンプレポ
リマー溶液：２０１．６重量部を添加した。その後、３
０分撹拌を行なった。得られた組成物は白濁した安定な
水分散体であった。Synthesis of aqueous unsaturated double bond-containing polymer composition N, under air flow, equipped with a thermometer, stirrer, and condenser dropping funnel 1
380 parts by weight of deionized water and 6 parts by weight of ethylenediamine were added to a reaction vessel No. 12, and while stirring, 201.6 parts by weight of the above urethane prepolymer solution was added. After that, 3
Stirring was performed for 0 minutes. The resulting composition was a cloudy, stable aqueous dispersion.
水性分散体組成物の合成
Ｎ、気流下、温度計、撹拌機、コンデンサー滴下ロート
を備えたｌＱの反応容器に上記水性不飽和二重結合含有
高分子組成物：５８７．６重量部を加え、次に、過硫酸
カリウム水溶液（過硫酸カリウム／脱イオン水＝ １／
４７４）：４０１重量部を加え、よく撹拌する。次に、
９０℃まで昇温し、メチルメタクリレ−１２９２重量部
とｎ−ブチルアクリレート＝９２重量部のモノマー混合
液を１時間で滴下導入した。滴下終了後、過硫酸カリウ
ム水溶液（過硫酸カリウム／脱イオン水＝１／３９）：
８重量部を添加し、さらに１時間撹拌を継続した。Synthesis of aqueous dispersion composition 587.6 parts by weight of the above aqueous unsaturated double bond-containing polymer composition was added to a 1Q reaction vessel equipped with a thermometer, a stirrer, and a condenser dropping funnel under a stream of air. Next, potassium persulfate aqueous solution (potassium persulfate/deionized water = 1/
474): Add 401 parts by weight and stir well. next,
The temperature was raised to 90°C, and a monomer mixture of 1292 parts by weight of methyl methacrylate and 92 parts by weight of n-butyl acrylate was introduced dropwise over 1 hour. After dropping, add potassium persulfate aqueous solution (potassium persulfate/deionized water = 1/39):
8 parts by weight were added, and stirring was continued for an additional hour.
冷却後、４００メツシユの濾過をし、安定な水性分散体
組成物を得た。After cooling, it was filtered through 400 meshes to obtain a stable aqueous dispersion composition.
実施例６
ウレタンプレポリマーの合成
Ｎ、気流下、温度計、撹拌機、コンデンサーを備えたＩ
Ｃの反応容器に、−（Ｎ、Ｎ−ジヒドロキジエチルアミ
ノ）プロピオン酸（ｍｐ： １０６℃）＝３２．２重量
部、トリエチメアミン：２０．２重量部、Ｎ−メチルピ
ロリドン：１００重量部を加え８０℃に加熱し溶解させ
る。次に、イソホロンジイソシアネート：２２２重量部
とポリプロピレングリコール（水酸基価：１１２．２、
分子量：１０００）：１８０重量部とポリプロピレング
リコール（水酸基価：５６．１．分子量：２０００）：
２００重量部を加え１０分間撹拌後、ジブチル錫ジラウ
レート：０．３３重量部を加える。次に、８０℃まで昇
温し、１時間反応させる。その後、６０℃まで冷却後、
ヒドロキシエチルメタクリレート：５．２重量部とヒド
ロキノンモノメチルエーテル：０．３３重量部を加え、
６０℃で２時間反応させる。冷却後、メチルメタクリレ
ート：６８重量部、ｎ−ブチルアクリレート二６７重量
部で希釈し、ウレタンプレポリマー溶液を得た。Example 6 Synthesis of urethane prepolymer N, under air flow, I equipped with thermometer, stirrer and condenser
-(N,N-dihydroxydiethylamino)propionic acid (mp: 106°C) = 32.2 parts by weight, triethymamine: 20.2 parts by weight, and N-methylpyrrolidone: 100 parts by weight were added to the reaction vessel C. Heat to ℃ to dissolve. Next, 222 parts by weight of isophorone diisocyanate and polypropylene glycol (hydroxyl value: 112.2,
Molecular weight: 1000): 180 parts by weight and polypropylene glycol (hydroxyl value: 56.1. Molecular weight: 2000):
After adding 200 parts by weight and stirring for 10 minutes, 0.33 parts by weight of dibutyltin dilaurate was added. Next, the temperature is raised to 80° C. and the mixture is reacted for 1 hour. Then, after cooling to 60℃,
Add 5.2 parts by weight of hydroxyethyl methacrylate and 0.33 parts by weight of hydroquinone monomethyl ether,
React at 60°C for 2 hours. After cooling, the mixture was diluted with 68 parts by weight of methyl methacrylate and 67 parts by weight of n-butyl acrylate to obtain a urethane prepolymer solution.
水性不飽和二重結合含有高分子組成物の合成Ｎ、気流下
、温度計、撹拌機、コンデンサー滴下ロートを備えた１
ｇの反応容器に脱イオン水：３０６重量部、ヒドラジン
−水和物＝４．５重量部を加え撹拌下、上記ウレタンプ
レポリマー溶／ｆＬ：１６２．８重量部を添加した。そ
の後、３０分撹拌を行なった。得られた組成物は白濁し
た安定な水分散体であった。Synthesis of aqueous unsaturated double bond-containing polymer composition N, under air flow, equipped with a thermometer, stirrer, and condenser dropping funnel 1
306 parts by weight of deionized water and 4.5 parts by weight of hydrazine hydrate were added to a reaction vessel (g), and while stirring, 162.8 parts by weight of the above urethane prepolymer solution/fL was added. Thereafter, stirring was performed for 30 minutes. The resulting composition was a cloudy, stable aqueous dispersion.
水性分散体組成物の合成
Ｎ、気流下、温度計、撹拌機、コンデンサー滴下ロート
を備えた！１２の反応容器に上記水性不飽和二重結合含
有高分子組成物：４７３．３重量部を加え、次に、過硫
酸カリウム水溶液（過硫酸カリウム／脱イオン水＝ １
／３４０）：３０７重量部を加え、よく撹拌する。次に
、９０℃まで昇温し、メチルメタクリレート：１０４．
２重量部とｎ−ブチルアクリレート：１０４重量部のモ
ノマー混合液を１時間で滴下導入した。滴下終了後、過
硫酸カリウム水溶液（過硫酸カリウム／脱イオン水−１
／６０）：１４．７重量部を添加し、さらに１時間撹拌
を継続した。冷却後、４００メツシユの濾過をし、安定
な水性分散体組成物を得た。Synthesis of aqueous dispersion composition N, under air flow, equipped with thermometer, stirrer, condenser dropping funnel! 473.3 parts by weight of the aqueous unsaturated double bond-containing polymer composition was added to No. 12 reaction vessel, and then an aqueous potassium persulfate solution (potassium persulfate/deionized water = 1
/340): Add 307 parts by weight and stir well. Next, the temperature was raised to 90°C, and methyl methacrylate: 104.
A monomer mixture of 2 parts by weight and 104 parts by weight of n-butyl acrylate was introduced dropwise over 1 hour. After dropping, add potassium persulfate aqueous solution (potassium persulfate/deionized water-1)
/60): 14.7 parts by weight was added, and stirring was continued for an additional hour. After cooling, it was filtered through 400 meshes to obtain a stable aqueous dispersion composition.
実施例７〜９
実施例３と同様に実施例４〜６で得られた水性分散体組
成物を実施例２で得られた水性分散体のかわりにメタリ
ック塗料を調整した。配合比は同じとする。水性クリヤ
ー塗料は実施例３のものを使用し塗装実験例１と同様の
評価を行った。表２に評価結果を示す。Examples 7 to 9 In the same manner as in Example 3, metallic paints were prepared using the aqueous dispersion compositions obtained in Examples 4 to 6 in place of the aqueous dispersion obtained in Example 2. The mixing ratio is the same. The water-based clear paint used in Example 3 was used, and the same evaluation as in Painting Experiment Example 1 was conducted. Table 2 shows the evaluation results.
比較例１
実施例３で得た水溶性アクリル樹脂１７０重量部にアル
ミニウム顔料を金属分で１０重量部撹拌混合し次いで脱
イオン水で希釈しＮｏ、４フオードカツプで２５〜３０
秒に希釈しメタリック塗料を得た。Comparative Example 1 170 parts by weight of the water-soluble acrylic resin obtained in Example 3 was stirred and mixed with 10 parts by weight of aluminum pigment, and then diluted with deionized water to give a No. 25 to 30
A metallic paint was obtained by diluting it in seconds.
塗装実験例１と同様に水性クリヤー塗料を塗装し評価を
行った。表−２に評価結果を示す。Aqueous clear paint was applied and evaluated in the same manner as in Painting Experiment Example 1. Table 2 shows the evaluation results.
評価方法は表−１と同じEvaluation method is the same as Table-1
Claims (1)
５０００のジオール化合物、 （ｂ）ジイソシアネート化合物、 （ｃ）分子内に少なくとも１個の活性水素を有しかつ両
性イオン基を有する化合物および（ｄ）分子内に活性水
素を有するエチレン性不飽和単量体 をイソシアネートリッチの条件下に反応させてなる両性
イオン基含有オリゴマーを１級及び／もしくは２級ポリ
アミンを含有する水もしくは親水性溶剤を含む水媒体に
分散してなる高分子組成物。 ２、請求項１記載の組成物５〜９５重量部（固形分）に
対しエチレン性不飽和単量体９５〜５重量部を配合し乳
化重合することにより得られる水性分散体。 ３、請求項２記載の水性分散体５〜９０重量部（固形分
）に対し、酸価１５〜１００および水酸基価３０〜２０
０を有する水溶性アクリル樹脂９５〜１０重量部（固形
分）および硬化剤を含有する水性塗料組成物。 ４、更に金属顔料を含む請求項３記載の水性塗料組成物
。[Claims] 1. (a) having a terminal hydroxyl group and a molecular weight of 100 to
5000 diol compound, (b) diisocyanate compound, (c) compound having at least one active hydrogen in the molecule and having a zwitterionic group, and (d) ethylenically unsaturated monomer having active hydrogen in the molecule. A polymer composition prepared by dispersing a zwitterionic group-containing oligomer obtained by reacting a zwitterionic group under isocyanate-rich conditions in water containing a primary and/or secondary polyamine or an aqueous medium containing a hydrophilic solvent. 2. An aqueous dispersion obtained by blending 95 to 5 parts by weight of an ethylenically unsaturated monomer to 5 to 95 parts by weight (solid content) of the composition according to claim 1 and subjecting the mixture to emulsion polymerization. 3. An acid value of 15 to 100 and a hydroxyl value of 30 to 20 for 5 to 90 parts by weight (solid content) of the aqueous dispersion according to claim 2.
An aqueous coating composition containing 95 to 10 parts by weight (solid content) of a water-soluble acrylic resin having a hardening agent. 4. The aqueous coating composition according to claim 3, further comprising a metal pigment.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339955A JPH072827B2 (en) | 1989-12-28 | 1989-12-28 | Polymer composition, aqueous dispersion and aqueous coating composition using the same as emulsifier |
| PCT/JP1990/001729 WO1991009895A1 (en) | 1989-12-28 | 1990-12-28 | Polymer composition, aqueous dispersion prepared by using the same as emulsifier, and water-base coating composition |
| AU70328/91A AU631964B2 (en) | 1989-12-28 | 1990-12-28 | Polymer composition, aqueous dispersion prepared by using the same as emulsifier, and water-base coating composition |
| KR1019910701016A KR920701294A (en) | 1989-12-28 | 1990-12-28 | Polymer compositions, aqueous dispersions and aqueous coating compositions prepared using the same as emulsifiers |
| EP91901565A EP0462287B1 (en) | 1989-12-28 | 1990-12-28 | Polymer composition, aqueous dispersion prepared by using the same as emulsifier, and water-base coating composition |
| CA002048653A CA2048653A1 (en) | 1989-12-28 | 1990-12-28 | Polymer compositions, aqueous dispersions and aqueous paint compositions by use thereof as emulsifiers |
| DE69029131T DE69029131T2 (en) | 1989-12-28 | 1990-12-28 | POLYMER COMPOSITION, USING ITS AQUEOUS DISPERSION AND EMPTYING COATING COMPOSITION, WATER-BASED |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1339955A JPH072827B2 (en) | 1989-12-28 | 1989-12-28 | Polymer composition, aqueous dispersion and aqueous coating composition using the same as emulsifier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200828A true JPH03200828A (en) | 1991-09-02 |
| JPH072827B2 JPH072827B2 (en) | 1995-01-18 |
Family
ID=18332350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1339955A Expired - Fee Related JPH072827B2 (en) | 1989-12-28 | 1989-12-28 | Polymer composition, aqueous dispersion and aqueous coating composition using the same as emulsifier |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0462287B1 (en) |
| JP (1) | JPH072827B2 (en) |
| KR (1) | KR920701294A (en) |
| AU (1) | AU631964B2 (en) |
| CA (1) | CA2048653A1 (en) |
| DE (1) | DE69029131T2 (en) |
| WO (1) | WO1991009895A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09328606A (en) * | 1996-06-07 | 1997-12-22 | Nippon Paint Co Ltd | Cold temperature curable resin composition and silicone-containing polymerizable surfactant |
| JPH1135657A (en) * | 1997-07-25 | 1999-02-09 | Kyoeisha Chem Co Ltd | Urethane unsaturated organooligomer and its production |
| JP2001354736A (en) * | 2000-06-12 | 2001-12-25 | Lock Paint Kk | Aqueous resin composition |
| JP2002302524A (en) * | 2001-04-06 | 2002-10-18 | Arakawa Chem Ind Co Ltd | Method for producing polyurethane resin aqueous dispersion |
| JP2008545050A (en) * | 2005-07-01 | 2008-12-11 | ザ シャーウィン−ウィリアムズ カンパニー | Multilayer coating system containing hydroxyl group-modified polyurethane dispersion binder |
| JP2012162677A (en) * | 2011-02-08 | 2012-08-30 | Fujifilm Corp | Coloring composition, colored radiation-sensitive composition, method of producing dye polymer, ink for inkjet, color filter and method of manufacturing the same, solid imaging device, and display device |
| JP2013518137A (en) * | 2010-01-21 | 2013-05-20 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Method for producing polyurethane-polyacrylate hybrid water-emulsifiable composition |
| JP2015196649A (en) * | 2014-03-31 | 2015-11-09 | 株式会社コーセー | Granules and cosmetic blending the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4129951A1 (en) * | 1991-09-10 | 1993-03-11 | Bayer Ag | COATING AGENTS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF COATINGS |
| KR970042827A (en) * | 1995-12-30 | 1997-07-26 | 김충세 | Water dispersible resin composition containing urethane oligomer |
| US7732006B2 (en) | 2006-08-28 | 2010-06-08 | Quest Optical, Incorporated | Coating composition and optical mar-resistant tintable coating |
| KR102356559B1 (en) * | 2019-11-25 | 2022-01-27 | 한국생산기술연구원 | Self-healable composition for forming polyurethane-based film and Articles comprising a layer coated with the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5736153A (en) * | 1980-08-13 | 1982-02-26 | Seiko Kagaku Kogyo Co Ltd | Aqueous dispersion of urethane-modified vinyl polymer, and preparation of said aqueous dispersion |
| GB2114587B (en) * | 1981-08-19 | 1984-11-07 | Sony Corp | Electron beam-curable resin |
| IT1153000B (en) * | 1982-07-01 | 1987-01-14 | Resem Spa | WATER DISPERSIONS OF POLYURETHANES FROM OLIGOURETANS WITH UNSATURATED TERMINAL GROUPS |
| US4558149A (en) * | 1983-12-16 | 1985-12-10 | Minnesota Mining And Manufacturing Company | Sulfonate-containing photopolymer systems |
| DE3437918A1 (en) * | 1984-10-17 | 1986-04-17 | Bayer Ag, 5090 Leverkusen | AQUEOUS OLIGOURETHANE DISPERSIONS WITH BUILT-IN, UNSATURATED GROUPS AND THEIR USE FOR THE PRODUCTION OF HIGH-GLOSSY PAINTS ON LEATHER FROM AQUEOUS PHASE |
| IT1187641B (en) * | 1985-03-21 | 1987-12-23 | Donegani Guido Ist | POLYURETHANE DENSE FILMS AND PROCESS FOR THEIR PREPARATION |
| DE4001841A1 (en) * | 1990-01-23 | 1991-07-25 | Bollig & Kemper | METHOD FOR PRODUCING POLYURETHANE DISPERSIONS |
-
1989
- 1989-12-28 JP JP1339955A patent/JPH072827B2/en not_active Expired - Fee Related
-
1990
- 1990-12-28 EP EP91901565A patent/EP0462287B1/en not_active Expired - Lifetime
- 1990-12-28 WO PCT/JP1990/001729 patent/WO1991009895A1/en active IP Right Grant
- 1990-12-28 KR KR1019910701016A patent/KR920701294A/en not_active Application Discontinuation
- 1990-12-28 CA CA002048653A patent/CA2048653A1/en not_active Abandoned
- 1990-12-28 AU AU70328/91A patent/AU631964B2/en not_active Ceased
- 1990-12-28 DE DE69029131T patent/DE69029131T2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09328606A (en) * | 1996-06-07 | 1997-12-22 | Nippon Paint Co Ltd | Cold temperature curable resin composition and silicone-containing polymerizable surfactant |
| JPH1135657A (en) * | 1997-07-25 | 1999-02-09 | Kyoeisha Chem Co Ltd | Urethane unsaturated organooligomer and its production |
| JP2001354736A (en) * | 2000-06-12 | 2001-12-25 | Lock Paint Kk | Aqueous resin composition |
| JP2002302524A (en) * | 2001-04-06 | 2002-10-18 | Arakawa Chem Ind Co Ltd | Method for producing polyurethane resin aqueous dispersion |
| JP2008545050A (en) * | 2005-07-01 | 2008-12-11 | ザ シャーウィン−ウィリアムズ カンパニー | Multilayer coating system containing hydroxyl group-modified polyurethane dispersion binder |
| JP2013518137A (en) * | 2010-01-21 | 2013-05-20 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Method for producing polyurethane-polyacrylate hybrid water-emulsifiable composition |
| JP2012162677A (en) * | 2011-02-08 | 2012-08-30 | Fujifilm Corp | Coloring composition, colored radiation-sensitive composition, method of producing dye polymer, ink for inkjet, color filter and method of manufacturing the same, solid imaging device, and display device |
| JP2015196649A (en) * | 2014-03-31 | 2015-11-09 | 株式会社コーセー | Granules and cosmetic blending the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR920701294A (en) | 1992-08-11 |
| EP0462287B1 (en) | 1996-11-13 |
| DE69029131T2 (en) | 1997-04-03 |
| WO1991009895A1 (en) | 1991-07-11 |
| CA2048653A1 (en) | 1991-06-29 |
| DE69029131D1 (en) | 1996-12-19 |
| EP0462287A1 (en) | 1991-12-27 |
| AU7032891A (en) | 1991-07-24 |
| EP0462287A4 (en) | 1992-06-24 |
| AU631964B2 (en) | 1992-12-10 |
| JPH072827B2 (en) | 1995-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5750613A (en) | Aqueous, crosslinkable binder dispersions having a low solvent content | |
| US5916965A (en) | Aqueous polyurethane resin and grafted polymer thereon | |
| TW254964B (en) | Stereolithographic seal and support structure for semiconductor wafer | |
| JP4204121B2 (en) | Self-crosslinking polyurethane polyacrylate hybrid dispersion | |
| JP2849969B2 (en) | Binder composition and its use for producing a coating or binder composition | |
| DE60129319T2 (en) | AQUEOUS, NETWORKED BINDER COMPOSITION AND COATING, LACQUER OR SEALANT COMPOSITION CONTAINING THIS BINDER COMPOSITION | |
| US20070100067A1 (en) | Aqueous coating composition | |
| JPH06234954A (en) | Water-based vehicle composition, coating medium containing said composition and use of said composition | |
| AT407045B (en) | AQUEOUS, SELF-CROSS-LINKING COPOLYMER DISPERSIONS, A METHOD FOR THE PRODUCTION AND THEIR USE IN BINDERS FOR VARNISHES | |
| JPH05208169A (en) | Method for applying multilayer laquer | |
| JPH03200828A (en) | Polymer composition, and aqueous dispersion and water-based coating composition containing the same as emulsifier | |
| JP2003524696A (en) | Waterborne paint for high solids baking lacquer | |
| WO1994003516A1 (en) | Polyacrylate and polyisocyanate-based water-dilutable coating agent | |
| US5585146A (en) | Two coat one bake coating method | |
| JPH024814A (en) | Copolymer containing isocyanate group and acid anhydride group and its production and use thereof as binder component | |
| EP0973816B1 (en) | Aqueous coating composition | |
| JP3814914B2 (en) | Water-based paint composition | |
| JP2006045452A (en) | Curable water-base resin composition | |
| JPH07252461A (en) | Binder based on cycloolefin copolymer peroxidized if necessary, its production, coating composition containing the copolymer, and use of the composition | |
| EP1263895A1 (en) | Aqueous acrylic coating composition | |
| JPS6034989B2 (en) | Water-dispersed thermosetting coating composition | |
| JPS5952911B2 (en) | Water-dispersed thermosetting coating composition | |
| JP2006052291A (en) | Method for producing aqueous resin dispersion | |
| JPH0488009A (en) | Thermosetting composition | |
| JPH10158523A (en) | Cross-link type aqueous emulsion composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |